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CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation 下载免费PDF全文
Dr. Yehua Jin Dr. Chien‐Hung Yeh Dr. Christian A. Kuttruff Dr. Lars Jørgensen Dr. Georg Dünstl Dr. Jakob Felding Dr. Swaminathan R. Natarajan Prof. Dr. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2015,54(47):14044-14048
Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained. 相似文献
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建立了微波等离子体原子发射光谱法(MP-AES)测定地质样品中的常量和微量元素的方法,四酸(盐酸+硝酸+高氯酸+氢佛酸)消解样品,得出了使用4200 MP-AES仪分析地化认证参考物质中常规金属元素(Ag,Cu,Ni,Pb和Zn)的结果,测定样品结果的相对标准偏差落在±10%范围内,另外,IEC和FLIC模型可成功校正光谱干扰。MP-AES仪无需使用乙炔等危险气体,极大提高了实验室安全性并显著降低了运行成本。MP-AES仪已成功应用于地化样品的分析中,结果准确可靠。 相似文献
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Joshua L. Brooks Phil Olsen Lijian Chen Andrew A. Rodriguez 《Tetrahedron letters》2017,58(11):1050-1052
Herein, we describe the isolation and characterization of a UnyLinker dimer which, if left uncontrolled, can become incorporated in oligonucleotide products. The dimer is formed as a result of an unusual intermolecular osmium-catalyzed etherification. We demonstrate that by simply replacing H2O2 as the co-oxidant with NMO, none of the UnyLinker dimer impurity is formed. 相似文献
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The thioether functionalized aminosilanes Me2Si(NH‐C6H4‐2‐SR)2 (R = Ph, Me) were lithiated with nBuLi and subsequently reacted with AgCl in the presence of PMe3 or with [AuCl(PMe3)]. In the case of Me2Si(NH‐C6H4‐2‐SPh)2 the dinuclear complexes [M2{Me2Si(NC6H4‐2‐SPh)2}(PMe3)2] (M = Ag; Au) were isolated. The analogous reactions starting from Me2Si(NH‐C6H4‐SMe)2 afforded the dinuclear gold complex [Au2{Me2Si(NC6H4‐2‐SMe)2}(PMe3)2] and the tetranuclear silver complex [Ag4{Me2Si(NC6H4‐2‐SMe)2}2(PMe3)2]. In the dinuclear compounds of the type [M2{Me2Si(NC6H4‐2‐SR)2}(PMe3)2], each of the silylamide N atoms is connected to a M(PMe3) group to give a nearly linear N–M–P arrangement with Ag–N and Au–N bonds in the range of 212.0(4)–213.3(4) pm and 205.3(3)–208.1(9) pm, respectively. [Ag4{Me2Si(NC6H4‐2‐SMe)2}2(PMe3)2] consists of a central Si2N4Ag2 ring with linearly coordinated Ag atoms (Ag‐N: 223.1(4)–222.1(4) pm) and two peripheral Ag(PMe3) units, which are connected to the amido N atoms in a chelating mode. The relatively short transannular Ag ··· Ag separation (277.6(1) pm) within the Si2N4Ag2 ring hints for argentophilic interactions. The peripheral Ag atoms are three coordinated with Ag–N distances of 233.9(4)–242.8(4) pm. 相似文献
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Dr. Tian Qin Dr. Lara R. Malins Jacob T. Edwards Rohan R. Merchant Alexander J. E. Novak Jacob Z. Zhong Riley B. Mills Ming Yan Dr. Changxia Yuan Dr. Martin D. Eastgate Prof. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2017,56(1):260-265
Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N ‐hydroxyphthalimide (NHPI) based redox‐active esters were found to be convenient starting materials for simple, thermal, Ni‐catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH3) or an electron‐deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry. 相似文献
7.
Simon Sengupta Philipp Schüler Dr. Helmar Görls Dr. Phil Liebing Dr. Sven Krieck Prof. Matthias Westerhausen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(50):e202201359
The in situ Grignard Metalation Method (iGMM) is a straightforward one-pot procedure to quickly produce multigram amounts of Hauser bases R2N-MgBr which are valuable and vastly used metalation reagents and novel electrolytes for magnesium batteries. During addition of bromoethane to a suspension of Mg metal and secondary amine at room temperature in an ethereal solvent, a smooth reaction yields R2N-MgBr under evolution of ethane within a few hours. A Schlenk equilibrium is operative, interconverting the Hauser bases into their solvated homoleptic congeners Mg(NR2)2 and MgBr2 depending on the solvent. Scope and preconditions are studied, and side reactions limiting the yield have been investigated. DOSY NMR experiments and X-ray crystal structures of characteristic examples clarify aggregation in solution and the solid state. 相似文献
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Triphenylphosphine/carbon tetrachloride and triphenyl-phosphine/N-bromosuccinimide were found to be very effective for β-lactam formation from β-amino acids in acetonitrile. 相似文献
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